Sorbent devices

ABSTRACT

Sorbent material sheets provide for enhanced performance in vapor adsorbing applications over conventional canisters and other emissions control equipment. The sorbent material sheets can be formed as part of a small, lightweight canister, or can be integrated into a fuel tank. The sorbent material sheets can also be used as part of an onboard refueling vapor recovery system to control volatile organic compound emissions from fuel tanks of gasoline vehicles, such as automobiles.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.62/713,894 filed Aug. 2, 2018 and U.S. Provisional Application No.62/735,436 filed Sep. 24, 2018. The disclosures of each of theseapplications are incorporated herein by reference.

BACKGROUND

Evaporative emissions from gasoline and other liquid hydrocarbon fuelsare a significant source of air pollution because the varioushydrocarbons contained in the fuels can form photochemical smog onexposure to sunlight. The compounds of this smog and the hydrocarbonsthemselves cause degrading health effects in humans and animals as wellas environmental damage. Evaporative emissions are especiallyproblematic during vehicle refueling because the “empty” fuel tank isactually filled with fuel vapors, and the act of filling the tank withliquid fuel displaces the vapors from the tank. Evaporative emissionsalso occur when the fuel within the tank is heated, such as from hotambient conditions or from nearby hot exhaust system components. Withoutcontrols, fuel vapors would be released as pollution into theatmosphere.

In the automotive sector, gasoline vapors are typically recovered duringrefueling by an Onboard Refueling Vapor Recovery (ORVR) canister system.These devices include multiple components which are designed to capturethe displaced vapors from gasoline refueling and allow the engine toburn them at a later time. Vapors remain sealed within the fuel tank byspecially designed tanks and fuel filler neck, and excess vapor iscaptured and adsorbed within a chemical canister. During engineoperation, the Engine Control Unit (ECU) permits adsorbed vapors to bereleased from the canister and into the engine fuel system, burning thegasoline vapors as normal and permitting the canister to be used again.

While ORVR systems have been successful in reducing vapor emissions,they still have drawbacks. The canisters are filled with loose adsorbentparticles such as activated carbon or charcoal, which can be messy tohandle and package. These canisters are bulky and heavy because theadsorbent particles cannot physically support themselves, and becausestringent emissions regulations now prohibit the release of even smallamounts of vapor emissions, which requires higher adsorbent capacity.Manufacturing, maintenance and disposal of the canisters is alsocumbersome because of the loose adsorbent particles, and the complexityof ORVR devices increases the cost of each vehicle while cutting intovaluable passenger and cargo space. With automakers demanding lighterweights from all components to meet increasing fuel efficiency targets,as well as cost reductions and greater passenger and cargo space, thereis a need for new ORVR devices and that are smaller, lighter, simpler,and more cost effective, while still complying with stricter emissionstargets.

Recent stricter emissions targets are particularly challenging. In theUnited States, this is driven by the adoption of the Low EmissionVehicle (LEV) III standards in California and subsequent equivalentstandards by the Environmental Protection Agency (EPA). Among otherfeatures, these regulations significantly lower the allowableevaporative emissions from ORVR systems, requiring not only theinclusion of a sorbent that has high overall adsorptive capacity, butalso a sorbent that has high overall retention to ensure that evenminute quantities of evaporative emissions are avoided. These minutequantities are known as “bleed” emissions.

The conventional solution to these emissions regulations is to include alarge chamber filled with a high capacity sorbent, followed by a muchsmaller “scrubber” chamber that has a small amount of low retentivitycarbon. The design of the smaller chamber conventionally includesdelicate carbon monoliths to increase the surface area of the carbon andlower gas velocities. Examples of this approach include U.S. Pat. Nos.9,732,649 and RE38,844, both of which are hereby incorporated byreference in their entirety. There is a need for evaporative emissionscontrols that avoid the problems and complexity of prior art solutionswhile still delivering improved performance.

SUMMARY

In one embodiment, the invention discloses sorbent material sheets thathave improved performance over the equivalent amount of adsorbentcompound provided as a powder.

In another embodiment, the invention discloses sorbent material sheetsenclosed within a housing.

In another embodiment, the invention discloses sorbent material sheetsthat omit the housing and which are instead contained directly within afuel tank.

In another embodiment, the invention discloses an emissions controlsystem, such as an ORVR which includes sorbent material sheets. Thesorbent material sheets within the ORVR may be enclosed within a housingor the housing may be omitted.

The invention is also directed to the embodiments listed below:

Embodiment 1—A vapor adsorbing canister comprising: a first sorbent, asecond sorbent, and wherein during an adsorption or a desorptionoperation, the linear velocity of gases is higher in the second sorbentthan in the first sorbent, and wherein the first sorbent and the secondsorbent each individually have an incremental adsorption capacity ofgreater than 35 g n-butane/L between vapor concentrations of 5 vol. %and 50 vol. % n-butane.

Embodiment 2—The vapor adsorbing canister of embodiment 1, wherein eachof the first sorbent and the second sorbent include a binder thatcomprises polytetrafluoroethylenes (PTFE or TEFLON), polyvinylidenefluorides (PVF₂ or PVDF), ethylene-propylene-diene (EPDM) rubbers,polyethylene oxides (PEO), UV curable acrylates, UV curablemethacrylates, heat curable divinyl ethers, polybutylene terephthalate,acetal or polyoxymethylene resin, fluoroelastomers, perfluoroelastomers(FFKM) and/or tetrafluoro ethylene/propylene rubbers (FEPM), aramidpolymers, para-aramid polymers, meta-aramid polymers, poly trimethyleneterephthalate, ethylene acrylic elastomers, polyimide, polyamide-imides,polyurethanes, low density and high density polyethylene, polypropylene,biaxially oriented polypropylene (BoPP), polyethylene terephthalate(PET), biaxially oriented polyethylene terephthalate (BoPET),polychloroprene, or copolymers or combinations thereof, and wherein thebinder of the first and the second sorbent is the same or different.

Embodiment 3—The vapor adsorbing canister of embodiments 1-2, whereinthe first sorbent and the second sorbent each individually include lessthan or equal to about 20 wt. % of binder.

Embodiment 4—The vapor adsorbing canister of embodiment 3, wherein thefirst sorbent and the second sorbent each individually include greaterthan or equal to about 80 wt. % of sorbent material.

Embodiment 5—The vapor adsorbing canister of embodiments 1-2, whereinthe first sorbent and the second sorbent each individually include lessthan or equal to about 10 wt. % of binder.

Embodiment 6—The vapor adsorbing canister of embodiment 5, wherein thefirst sorbent and the second sorbent each individually include greaterthan or equal to about 90 wt. % of sorbent material.

Embodiment 7—The vapor adsorbing canister of embodiments 1-6, whereinthe second sorbent is in the form of a sheet.

Embodiment 8—The vapor adsorbing canister of embodiments 1-6, whereinthe second sorbent is in the form of a sheet that is corrugated,textured, folded, has apertures, wrapped in an “S” shape, in a convex“C” shape, in a concave “C” shape, rolled, has spacers between multiplesheets, and combination of the above features.

Embodiment 9—The vapor adsorbing canister of embodiments 1-6 or 8,wherein the second sorbent is in the form of a sheet, said sheetincluding sorbent particles having an average particle diameter of about0.001 mm to about 0.2 mm.

Embodiment 10—The vapor adsorbing canister of embodiments 1-6 or 8-9,wherein the second sorbent is in the form of a sheet having raisedand/or depressed portions.

Embodiment 11—The vapor adsorbing canister of embodiment 10, wherein theraised and/or depressed portions are present on adjacent sheets and arenested.

Embodiment 12—The vapor adsorbing canister of embodiment 10, wherein theraised and/or depressed portions are present on adjacent sheets and arenot nested.

Embodiment 13—The vapor adsorbing canister of embodiments 1-6 or 8-12,wherein the second sorbent is in the form of a sheet having a voidvolume of about 10% or more.

Embodiment 14—The vapor adsorbing canister of embodiments 1-6 or 8-13,wherein the second sorbent is in the form of a sheet having a density ofabout 0.08 g/cm³ to about 1.5 g/cm³.

Embodiment 15—The vapor adsorbing canister of embodiments 1-14, whereinthe first sorbent and the second sorbent are each separately selectedfrom the group consisting of activated carbon, carbon nanotubes,graphenes, natural and synthetic zeolite, silica, silica gel, alumina,zirconia, diatomaceous earths, and combinations thereof

Embodiment 16—The vapor adsorbing canister of embodiments 1-15, furthercomprising a housing.

Embodiment 17—The vapor absorbing canister of embodiment 16, wherein thehousing is flexible.

Embodiment 18—The vapor adsorbing canister of embodiments 16-17, whereinthe housing is selected from the group consisting ofpolytetrafluoroethylenes (PTFE or TEFLON), polyvinylidene fluorides(PVF₂ or PVDF), ethylene-propylene-diene (EPDM) rubbers, polyethyleneoxides (PEO), UV curable acrylates, UV curable methacrylates, heatcurable divinyl ethers, polybutylene terephthalate, acetal orpolyoxymethylene resin, fluoroelastomers perfluoroelastomers (FFKM)and/or tetrafluoro ethylene/propylene rubbers (FEPM), aramid polymers,para-aramid, meta-aramid polymers, poly trimethylene terephthalate,ethylene acrylic elastomers, polyimide, polyamide-imides, polyurethanes,low density and high density polyethylene, polypropylene, biaxiallyoriented polypropylene (BoPP), polyethylene terephthalate (PET),biaxially oriented polyethylene terephthalate (BoPET), polychloroprene,copolymers thereof, and combinations thereof

Embodiment 19—The vapor adsorbing canister of embodiments 1-18, furthercomprising at least one structure selected from tubes, inlet ports,outlet ports, sensors, valves, and fluid channels.

Embodiment 20—An onboard refueling vapor recovery apparatus comprisingthe vapor adsorbing canister of embodiments 1-19.

DETAILED DESCRIPTION

Before the present compositions and methods are described, it is to beunderstood that this invention is not limited to the particularprocesses, compositions, or methodologies described, as these may vary.It is also to be understood that the terminology used in the descriptionis for the purpose of describing the particular versions or embodimentsonly, and is not intended to limit the scope of the present invention,which will be limited only by the appended claims. Unless definedotherwise, all technical and scientific terms used herein have the samemeaning as commonly understood by one of ordinary skill in the art.Although any methods and materials similar or equivalent to thosedescribed herein can be used in the practice or testing of embodimentsof the present invention, the preferred methods, devices, and materialsare now described. All publications mentioned herein are incorporated byreference in their entirety. Nothing herein is to be construed as anadmission that the invention is not entitled to antedate such disclosureby virtue of prior invention.

It must also be noted that as used herein and in the appended claims,the singular forms “a,” “an,” and “the” include plural reference unlessthe context clearly dictates otherwise. Thus, for example, reference to“a combustion chamber” is a reference to “one or more combustionchambers” and equivalents thereof known to those skilled in the art, andso forth.

As used herein, the term “about” means plus or minus 10% of thenumerical value of the number with which it is being used. Therefore,about 50% means in the range of 45%-55%.

As used herein, the term “sorbent material” is meant to encompass allknown materials from any source that are capable of absorbing and/oradsorbing liquids and/or gases. For example, sorbent materials include,but are not limited to, activated carbon, carbon nanotubes, graphenes,natural and synthetic zeolite, silica, silica gel, alumina, zirconia,and diatomaceous earths. As is known in the art, adsorption is theprocess by which molecules adhere to the surface of a material bychemical forces. In contrast, absorption is the process where a materialis retained by another.

As used herein, descriptions and claims of multiple sorbent materialsheets mean that there are multiple, separated sheets, with sides and/orsurfaces in proximity to each other. Alternatively, descriptions andclaims of multiple sorbent material sheets mean that there is only asingle sheet, but that it has been wound or folded over on itself toyield a stacked, wound, or otherwise constructed mass of sheets withsides and/or surfaces in proximity to each other. The term alsoenvisions that multiple sheets are stacked together and then wound orotherwise folded over, forming alternating layers in a single mass.

As used in the context of the sorbent or sorbent material or sorbentmaterial sheets, the term surface means the outer boundary of thatindividual component. Even more specifically, in the context of thesorbent material sheets, the term surface means the largest planar facesof the sheets, which when rolled or stacked face each other orthemselves. In a sheet, the surface is the portion that is significantlylarger than the thickness of the sheet.

Embodiments of the invention are directed to devices containing one ormore sheets of sorbent material, sorbent material sheets, and methodsfor making sorbent material sheets and devices containing these sheets.In various embodiments, the sorbent material sheets may be composed of asorbent material and a binder and have a thickness of less than about 1mm, or a thickness of less than about 2 mm. The devices of variousembodiments may include a housing and one or more sorbent materialsheets. In some embodiments, the devices may have a void fraction ofabout 10% or more of the total volume of the housing.

Further embodiments are directed to sorbent devices described in U.S.patent application Ser. No. 15/885,317 filed on Jan. 31, 2018, theentirety of which is hereby incorporated by reference.

The Sorbent Material Sheets

The sorbent material sheets of the invention may include any of thesorbent materials described above including, but are not limited to,activated carbon, carbon nanotubes, graphenes, natural and syntheticzeolite, silica, silica gel, alumina, zirconia, and diatomaceous earths,and in certain embodiments, the sorbent material sheets may be composedof activated carbon. The sorbents may be used alone or in combination.

The activated carbon may be of various grades and types selected basedon performance requirements, cost, and other considerations. Theactivated carbon may be granular from reagglomerating a powder, granularfrom crushing or sizing nutshells, wood, coal or pellets created byextrusion, or activated carbon in powdered form. The activated carbonmay be formed by processes of carbonization and activated. The rawmaterial, such as wood, nutshell, coal, pitch, etc. is oxidized anddevolatized, with steam and/or carbon dioxide gasified to form the porestructure in the activated carbon which is useful for adsorption. Theinitial oxidation and devolatilization process may include a chemicaltreatment with a dehydrating chemical, such as phosphoric acid, sulfuricacid, sodium hydroxide, potassium hydroxide, and combinations of those.

A variety of activation processes are known in the art. The most usefulprocesses for providing activated carbon for the sorbent material sheetsof the claimed invention involve a step of providing wood and/or woodbyproduct, acid treating the wood and/or wood byproducts by exposure tophosphoric acid, and carbonizing the wood and/or wood byproducts usingsteam and/or carbon dioxide gasification. This process results inactivated carbon particles having the highest butane working capacity(“BWC”), which is a measure of activated carbon performance. Moredetails of the BWC testing and results are described in the Examples.

The activated carbon may be formed from materials including bagasse,bamboo, coconut husks, peat, wood such as hardwood and softwood sourcesin the form of sawdust and scrap, lignite, synthetic polymers, coal andcoal tar, petroleum pitch, asphalt and bitumen, corn stalks and husks,wheat straw, spent grains, rice hulls and husks, nutshells, andcombinations thereof

The sorbent material sheets may further include one or more binders.Embodiments are not limited to particular binders, which can includepolytetrafluoroethylenes (PTFE or TEFLON), polyvinylidene fluorides(PVF₂ or PVDF), ethylene-propylene-diene (EPDM) rubbers, polyethyleneoxides (PEO), UV curable acrylates, UV curable methacrylates, heatcurable divinyl ethers, polybutylene terephthalate, acetal orpolyoxymethylene resin, fluoroelastomers such as perfluoroelastomers(FFKM) and tetrafluoro ethylene/propylene rubbers (FEPM), aramidpolymers such as para-aramid and meta-aramid polymers, poly trimethyleneterephthalate, ethylene acrylic elastomers, polyimide, polyamide-imides,polyurethanes, low density and high density polyethylene, polypropylene,biaxially oriented polypropylene (BoPP), polyethylene terephthalate(PET), biaxially oriented polyethylene terephthalate (BoPET),polychloroprene, and copolymers and combinations thereof. The binderscan be thermoplastic or thermosetting as conditions require, and caninclude mixtures of thermoplastic and thermosetting compounds.

The amount of binder may be about 1% to about 30% by weight of the totalcomposition, and in certain embodiments, the amount of binder may beabout 1% to about 20% by weight or about 2% to about 10% by weight ofthe total composition, or any individual amount or range encompassingthese example amounts. The binder may be present in the amount of about1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%,about 15%, about 16%, about 17%, about 18%, about 19%, about 20% or anyrange made of any two or more of the above amounts, all of which aremeasured by weight of the total composition. In some embodiments, thesorbent material sheets may include a solvent, which may generally bepresent in small, residual, amounts of, for example, less than 10%, lessthan 5%, or less than 2% and greater than about 0.1% or 0.2% by weight.In particular, in some embodiments the sorbent material sheets may haveno (0%) solvent

In some embodiments, the sorbent material sheets have a thickness ofless than about 2 mm, less than about 1.8 mm, less than about 1.6 mm,less than about 1.4 mm, less than about 1.2 mm, less than about 1.0 mm,about 0.01 mm to about 2 mm, about 0.01 mm to about 1.8 mm, about 0.1 mmto about 1.6 mm, about 0.01 mm to about 1.4 mm, about 0.01 mm to about1.2 mm, about 0.01 mm to about 1.0 mm, about 0.02 mm to about 0.90 mm,about 0.05 to about 0.95 mm, about 0.05 to about 0.90 mm or anyindividual thickness or range encompassed by these example ranges. Thesorbent material sheets of various embodiments may have a density ofabout 0.05 g/cm³ to about 2.0 g/cm³, and in other embodiments, thesorbent material sheets may have a density of 0.08 g/cm³ to about 1.5g/cm³, about 0.1 g/cm³ to about 1.3 g/cm³, or any density or rangeencompassed by these example ranges. The density is calculated first bymeasuring the thickness of a given square or circular piece of sheetwith a micrometer, multiplying by the surface area to obtain the volume,and weighing the piece to obtain the density (weight / volume).The BWCfor each sorbent material sheet may be greater than about 10 g/100 cm³,and in some embodiments, the BWC may be from about 7.0 g/100 cm³ toabout 30 g/100 cm³, about 8.0 g/100 cm³ to about 25 g/100 cm³, about 10g/100 cm³ to about 20 g/100 cm³, about 10 g/100 cm³ to about 15 g/100cm³, about 11 g/100 cm³ to about 15 g/100 cm³, about 12 g/100 cm³ toabout 15 g/100 cm³ or any individual BWC or range encompassed by theseexample ranges. In other examples, the BWC may be about 9 g/100 cm³ toabout 15 g/100 cm³, about 12 g/100 cm³ to about 20 g/100 cm³, about 13g/100 cm³ to about 20 g/100 cm³, about 14 g/100 cm³ to about 20 g/100cm³, or about 15 g/100 cm³ to about 20 g/100 cm³. It is alsocontemplated that any of the endpoints of the above ranges may becombined to form new and distinct ranges.

The sorbent material sheets of the present invention have higherperformance as measured by the BWC than conventional sorbent materialswhich are provided in powders or other particle forms.

The sorbent material sheets of embodiments can be made by any suitableprocess. In some embodiments, sorbent material sheets can be made bypulverizing granular or pelletized sorbent material to a powder, mixingthe powder with a binder to form a mixture, heating and blending themixture, and rolling the mixture to form the sorbent material sheet. Thestep of pulverizing may produce sorbent particles having an averageparticle diameter of about 0.001 mm to about 0.2 mm, about 0.005 mm toabout 0.1 mm, about 0.01 mm to about 0.075 mm, or any individualparticle diameter or range encompassed by these example ranges, and incertain embodiments, the pulverized sorbent particles may have anaverage particle diameter of about 0.001 mm to about 0.01 mm. The stepof mixing the powder with a binder may include mixing the sorbentparticle powder with about 2% to about 20% by weight or about 2% toabout 10% by weight of the total composition, or any individual amountor range encompassed by these example ranges. Heating can be carried outat any temperature sufficient to remove residual solvent such as, forexample, about 50° C. to about 200° C.

The sorbent material sheet of the invention may include variousdistributions of different sized particles to increase the packingefficiency of the powder within the sorbent material sheets. Theselection of different sized particles can also improve rheologicalproperties of the powder and surrounding binders, which allows improvedmixing and uniform particle distribution before formation of the sorbentmaterial sheets. In some embodiments, the particles of the sorbentmaterial sheet may have a single particle size distribution, and inother embodiments, the particles may have two different particle sizedistributions. In further embodiments, the particle may have at leastthree different particle size distributions.

The mean particle sizes of at least two different particle populations,each having a particular size distribution, may be selected so that theyhave a ratios of between about 1:1 and about 1:15: In other embodiments,the mean particle sizes of the two different particle populations mayhave a ratio of about 1:2 to about 1:10. The mean particle sizes mayalso have a ratio of about 1:2 to about 1:5, or combinations of any ofthe above listed ratios.

The sorbent material sheets have significantly higher sorbent capacitythan prior art fuel vapor recovery canisters for a given volume and/orweight. This capability can be utilized in various ways. In someembodiments, the sorbent material sheets can provide enhanced pollutioncontrols in jurisdictions where such high levels of control arerequired. In other embodiments, the overall size, cost, and weight ofthe ORVR can be reduced for a specific level of performance. In furtherembodiments, an ORVR adsorption device can be designed which hasincreased performance over conventional adsorption canisters, therebyallowing the designer to omit costly and complex returnless fuel pumpsystems which would otherwise be required to reduce evaporativeemissions. Higher performance adsorption devices may also render activecondensing vapor systems unnecessary, which avoids the size, weight, andcost of compressor pumps and condensate storage tanks. It should beunderstood, however, that the ORVR adsorption device using the sorbentmaterial sheets of the invention can also be combined with these devicesfor exceptionally high performance and a minimal size, weight, and costpenalty over conventional systems.

The sorbent material sheets may be configured together in a variety ofways depending on the physical space that they must conform to, therequired device performance, and the features which are included inproximity to the sheets. In some embodiments, the sheets may becorrugated, include folds, and/or include holes or apertures to increasethe surface area of the sorbent material sheets that is exposed to thepassing fluid, therefore increasing performance for a given total sheetsurface area. The various corrugations, folds, holes, and apertures canalso be sized and placed to make way for internal and external features,such as fluid channels, tubing, sensors, and valves. The folds of thesorbent material sheets may take a variety of forms, such as a spiralwrapped configuration in either a cylindrical or elliptical form. Thefolds may also be in the form of an “S” shape, or a convex or concave“C” shape depending on the required device dimensions and/or any otherrequired internal or external features. The sorbent material sheets mayalso be stacked in a flat or curved configuration, and the stackedsheets may be square, rectangular, circular, oval, or other irregularshape as needed to fit the space intended. This, in combination with thehousing features discussed below, enables devices formed from thesorbent material sheets to fit in smaller, more irregularly shapedspaces than prior art canister devices, which maximizes vehicle interiorspace.

In addition to the above described configurations, the sorbent materialsheets may also have surface features. In some embodiments, the sorbentmaterial sheets may include raised portions, and in other embodiments,the sorbent material sheets may include depressed portions. Thesesurface features may be combined within the same sheet. The inclusion ofraised and/or depressed portions in the sheets may be utilized to formvarious configurations between the sheets as they are stacked, wrapped,and so forth. For instance, the sheets can be aligned so that the raisedand/or depressed portions nest with each other, which brings theadjacent sheets closer together. The sheets can also be aligned so thatthe raised and/or depressed portions do not nest with each other, whichforms a gap between the adjacent sheets. The alignment can be used toform various open and closed channels for vapor adsorption between thesheets.

Sorbent Material Sheet Product

The sorbent material sheets described above are combined into a sorbentmaterial sheet product. The combination of the sorbent material sheetstakes advantage of one or more of the above described features, such asincreased surface area/volume ratio, reduced void space, improvedsorbent performance, etc. In general, the individual sorbent materialsheets are arranged next to each other to form a sorbent material sheetproduct that comprises sheets that are stacked, rolled, wound, folded,and/or laminated such that the surfaces of the sorbent material sheetsare in close proximity to, or adjacent to each other. Whatever thearrangement, the goal is to maximize the surface area of the sheetsexposed to the vapor, fluid, and/or gas stream and thus the performanceof the sorbent material sheets.

Stacked Sorbent Material Sheet Product: The stacked sorbent materialsheet product of the invention comprises two or more sorbent sheets eachdefining an upper surface and a lower surface, and having a knowncombined total surface area, wherein each sorbent sheet comprises asorbent material and a binder; where adjacent sorbent sheets are stackedand arranged such that adjacent upper and lower surfaces aresubstantially congruent with each other, and aligned to allow fluid flowat least between adjacent upper and lower surfaces.

The term substantially parallel as used in the context of a stackedsorbent material sheet product means that the sheets maintain the samedistance apart over their entire area, but with exceptions made forvarious physical characteristics and features. These exceptions thatstill fall within the scope of substantially parallel include but arenot limited to differences due to variations in components such asspacers, sensors, apertures, tubing, ports, valves, channels,corrugations, pleats, folds, deformation encountered duringmanufacturing or operation, deformation due to the shape or pressuresapplied by or through the external housing, different wrappingtechniques such as to seal the peripheries of the sheets, and so forth.

Performance improvements of the stacked sorbent material sheet productof the invention can be measured as the performance of the producthaving a given amount of activated carbon versus the performance of thatsame amount and grade of activated carbon if provided within a canisterin a pelletized or powdered form. In some embodiments, the stackedsorbent sheet product has a BWC that is about 3% higher, about 5%higher, about 7% higher, about 9% higher, about 10% higher, about 12%higher, about 14% higher, and about 16% higher than the same volume andgrade of activated carbon within a canister in pelletized or powderedform. Ranges based on these amounts are also contemplated, such asperformance that is between about 5-14% higher, between about 5-10%higher, between about 10-16% higher, and so forth.

It should be noted that these improvements are only measured as betweenthe volumes of the pelletized or powdered activated carbon and thestacked sorbent material sheet product, without accounting for otherimprovements of the stacked sorbent material sheet product. One keydifference, described above, is the omission of a rigid canister bodythat would otherwise be required. The omission of the rigid canisterbody, which is needed in prior art systems involving pelletized orpowdered activated carbon because the loose activated carbon cannotsupport itself, drives further weight savings and therefore even furtherperformance for a given weight.

The stacked sorbent sheet product has a BWC at least 10% higher than theBWC of a pelletized/powdered form of the same volume of the sorbentmaterial in the sorbent sheet. The stacked sorbent sheet product has aBWC greater than about 10 g/100 cm³. The stacked sorbent sheet producthas a BWC of about 7.0 g/100 cm³ to about 30 g/100 cm³, or greater thanabout 12 g/100 cm³, or greater than about 13 g/100 cm³, or greater thanabout 14 g/100 cm³, or greater than about 15 g/100 cm³, or greater than20 g/100 cm³. Ranges are also contemplated, such as about 10-20 g/cm³,about 10-12 g/cm³, about 10-14 g/cm³, about 12-14 g/cm³, about 12-15g/cm³, and about 15-20 g/cm³.

In some embodiments, the stacked sheets are held in a spaced apartrelationship which controls one or more of void volume, flow rate,pressure drop, and other characteristics. Such spacing is achieved insome embodiments where at least one of the two or more sorbent materialsheets is corrugated. The spacing can also be achieved with variousfolds in the sheets, and can also be achieved by the correspondingraised and/or depressed portions of the sheets which are aligned to formgaps between the sheet. If the sheets are arranged deliberately so thatthe raised and/or depressed portions of the sheets do not nest betweensheets, this results in additional spacing between the sheets andpermits fluid flow in those portions. If the sheets are arrangeddeliberately so that at least some raised and/or depressed portions nestbetween sheets, this results in a tighter fitting stack of sheets anddecreases the spacing between the sheets, with a corresponding decreaseor even stop in fluid flow. Combinations of these features can be usedto form stacked sorbent sheet products with directed regions or channelsfor fluid flow and barriers or edge seals to prevent fluid leakage.These features for fluid flow can also include holes, cuts, or aperturesthrough one or more of the sheets in the stacked sorbent sheet product.

Each sorbent sheet defines opposed lateral edges which are substantiallyparallel to fluid flow. The congruent lateral edges of adjacent sorbentsheets may be separate from each other, bound together or somecombination thereof. In this manner, the edges of the stacked sorbentmaterial sheet product may be sealed, partially sealed, or unsealed. Thesealed or unsealed nature can be chosen to achieve desired results suchas modifying fluid flow rate and/or patterns or other properties.

In some embodiments, the stacked sorbent material product yields a voidvolume of about 10% or more.

In some embodiments, each sorbent sheet has a density of about 0.08g/cm³ to about 1.5 g/cm³.

In some instances, the sorbent material sheet product comprises at leasttwo populations of sorbent material particles, wherein each of the atleast two populations have different average particle diameters. See theabove description of the bimodal particle size distribution which wasdiscussed with respect to the individual sorbent material sheets. Thesame distribution ratios as between populations of sorbent particles arecontemplated with respect to product formed of multiple sorbent materialsheets. In some instances, the density of the sorbent material particlesachieved by the at least two populations is greater than the densityachieved by either population alone. The inclusion of a bimodal particlesize distribution can also be used to improve the mechanical propertiesof the sorbent material sheet product because it makes the polymericsheets much more resistant to shear forces.

In some instances, a sorbent material sheet product comprises at leasttwo sorbent material sheets, each of which has a defined upper surfaceand lower surface which have a combined total surface area, and whereineach sorbent material sheet comprises a sorbent material and a binder,and wherein each sorbent material sheet is stacked and arranged suchthat adjacent upper and lower surfaces of the separate sheets aresubstantially parallel and are aligned to allow fluid flow at leastbetween the adjacent upper and lower surfaces.

In some embodiments, the sorbent material sheet product has a BWC valueof about 5%, about 10%, about 15%, about 20%, about 25%, about 30%,about 35%, about 40%, about 45%, and about 50% higher than the BWC ofthe same volume of sorbent material in pelletized or powdered forms.These can also be combined to form ranges, for example, between about5-25% higher. The invention also contemplates that these amounts are theendpoints on ranges, such as at least about 40% higher.

The sorbent material sheets in the sorbent material sheet product, maybe configured as being flat, wound in a spiral cylinder, wound in anelliptical form, wound in an elongate rectangular bar, folded, laminatedin an “S” shape, formed as concentric cylinders, formed as concentricellipses, formed as a concentric rectangular bar, or as combinations ofthese forms.

In some embodiments, the sorbent material sheet product will comprise asingle sorbent material sheet that is wound or rolled to achieve thedesired characteristics including, but not limited to density, voidspace, pressure drop, etc.

Wound/Rolled Sorbent Material Sheet Product: The sorbent material sheetproduct can also be wound or rolled as an alternative or in combinationwith stacked embodiments. A wound or rolled sorbent material sheetproduct comprises a sorbent sheet defining an upper surface and a lowersurface, and combined has a known total surface area, wherein thesorbent sheet comprises a sorbent material and a binder where thesorbent sheet is spiral wound to create adjacent sheet layers whichallow fluid flow around and between adjacent sheet layers.

Performance improvements of the rolled sorbent material sheet product ofthe invention can be measured as the performance of the product having agiven amount of activated carbon versus the performance of that sameamount and grade of activated carbon if provided within a canister in apelletized or powdered form. In some embodiments, the rolled sorbentsheet product has a BWC that is about 3% higher, about 5% higher, about7% higher, about 9% higher, about 10% higher, about 12% higher, about14% higher, and about 16% higher than the same amount and grade ofactivated carbon within a canister in pelletized or powdered form.Ranges based on these amounts are also contemplated, such as performancethat is between about 5-14% higher, between about 5-10% higher, betweenabout 10-16% higher, and so forth.

The rolled sorbent sheet product has a BWC at least 10% higher than theBWC of a pelletized/powdered form of the same amount by weight of thesorbent material in the sorbent sheet. The stacked sorbent sheet producthas a BWC greater than about 10 g/100 cm³. The stacked sorbent sheetproduct has a BWC of about 7.0 g/100 cm³ to about 30 g/100 cm³, orgreater than about 12 g/100 cm³, or greater than about 13 g/100 cm³, orgreater than about 14 g/100 cm³, or greater than about 15 g/100 cm³, orgreater than 20 g/100 cm³. Ranges are also contemplated, such as about10-20 g/cm³, about 10-12 g/cm³, about 10-14 g/cm³, about 12-14 g/cm³,about 12-15 g/cm³, and about 15-20 g/cm³.

A rolled sorbent sheet product as described herein has a generallycylindrical shape having a length substantially greater than itsdiameter, although any dimension can be employed, including conical, orfrustro-conical variations, as well as ellipsoids, or other shapes.

The density of the rolled sorbent sheet product may be computed based onthe formulas below:

$\begin{matrix}{{{Roll}\mspace{14mu} {Density}\mspace{14mu} {Calculations}\mspace{14mu} \left( {{US}\mspace{14mu} {units}} \right)}\mspace{11mu}} & \; & {{\rho \mspace{11mu} \left( \frac{lb}{{ft}^{3}} \right)} = {(3)*\frac{{BW}*L}{\left( {\frac{{OD}^{2}}{4} - \frac{{ID}^{2}}{4}} \right)*\pi}}} \\{{BW}\text{:}\mspace{14mu} {Basis}\mspace{14mu} {Weight}\mspace{14mu} \left( \frac{oz}{{yd}^{2}} \right)} & {L\text{:}\mspace{14mu} {Length}\mspace{14mu} {on}\mspace{14mu} {Roll}\mspace{14mu} ({yd})} & \; \\{{OD}\text{:}\mspace{14mu} {Outer}\mspace{14mu} {Roll}\mspace{14mu} {Diameter}\mspace{14mu} ({in})} & {{ID}\text{:}\mspace{14mu} {Inner}\mspace{14mu} {Roll}\mspace{14mu} {Diameter}\text{/}} & \; \\\; & {\mspace{45mu} {{Core}\mspace{14mu} {Diameter}\mspace{14mu} ({in})}} & \; \\{{W\text{:}\mspace{14mu} {Machine}\mspace{14mu} {width}\mspace{14mu} {or}}\mspace{14mu}} & {\rho \text{:}\mspace{14mu} {Roll}\mspace{14mu} {Density}\mspace{14mu} \left( \frac{lb}{{ft}^{3}} \right)} & \; \\{\mspace{45mu} {{roll}\mspace{14mu} {length}\mspace{14mu} ({in})}} & \; & \;\end{matrix}$ $\begin{matrix}{{Roll}\mspace{14mu} {Density}\mspace{14mu} {Calculations}\mspace{14mu} \left( {{SI}\mspace{14mu} {units}} \right)} & \; & {{\rho \mspace{11mu} \left( \frac{kg}{m^{3}} \right)} = {(1000)*\frac{{BW}*L}{\left( {\frac{{OD}^{2}}{4} - \frac{{ID}^{2}}{4}} \right)*\pi}}} \\{{BW}:{{Basis}\mspace{14mu} {Weight}\mspace{14mu} \left( \frac{g}{m^{2}} \right)}} & {L:{{Length}\mspace{14mu} {on}\mspace{14mu} {Roll}\mspace{14mu} (m)}} & \; \\{{OD}\text{:}\mspace{14mu} {Outer}\mspace{14mu} {Roll}\mspace{14mu} {Diameter}\mspace{14mu} ({mm})} & {{ID}\text{:}\mspace{14mu} {Inner}\mspace{14mu} {Roll}\mspace{14mu} {Diameter}\text{/}} & \; \\\; & {\mspace{45mu} {{Core}\mspace{14mu} {Diameter}\mspace{14mu} ({mm})}} & \; \\{{W\text{:}\mspace{14mu} {Machine}\mspace{14mu} {width}\mspace{14mu} {or}}\mspace{14mu}} & {\rho \text{:}\mspace{14mu} {Roll}\mspace{14mu} {Density}\mspace{11mu} \left( \frac{kg}{m^{3}} \right)} & \; \\{\mspace{45mu} {{roll}\mspace{14mu} {length}\mspace{14mu} ({mm})}} & \; & \;\end{matrix}$

The rolled sorbent sheet product may be wound to an average roll densityof about 80-1500 kg/m³, about 500-2000 kg/m³, about 750-1500 kg/m³,about 900-1200 kg/m³, about 900-1050 kg/m³, about 400-500 kg/m³, about500-600 kg/m³, about 500-550 kg/m³, about 600-650 kg/m³, about 650-700kg/m³, and about 700-750 kg/m³.

The rolled sorbent sheet product has a BWC greater than about 10 g/100cm³. In some embodiments, the rolled sorbent sheet product has a BWC ofabout 7.0 g/100 cm³ to about 30 g/100 cm³. The rolled sorbent sheetproduct may also have BWCs that are the same as the above describedsorbent sheet products which are not rolled.

Similar to the discussion above with respect to the stacked sorbentmaterial sheets, the wound or rolled sorbent material sheets may includemultiple particle size distributions or populations of the adsorbentpelletized or powdered activated carbon. The same ratios arecontemplated as discussed above. Similar to the discussion above, thisresults in greater performance because it enables a larger amount of theactivated carbon to be incorporated into the sheets which are formedinto the rolled sorbent sheet product.

As used herein, wound or rolled sorbent sheet products refer to any formof layering of one or more sorbent material sheets by winding, spiralwinding, concentric layering of tubular (of any cross-sectional shape,e.g. round, elliptical, square, triangular, rectangle, etc.) orcombination thereof. For example, a single sorbent material sheet may bespiral wound along its length to form a cylindrical-shaped rolledsorbent material sheet product. As another example, a plurality ofsorbent material sheets can be stacked and then wound together to form asimilar cylindrical shape. As another alternative, several sheets eachformed into a cylinder having a slightly different diameter from thenext can be arranged such that they from concentric rings incross-section of a similarly sized cylinder. Various combinations ofthese and other arrangements may be used to fill the space within anyshape of housing or canister, as described elsewhere herein.

As used in the context of a wound or rolled sorbent material sheet orsheets, the term substantially parallel is used to mean that at aminute, infinitely small dimension, the two sheets or portions of thesame sheets are the same distance from each other in all directions.However, it is also understood that in the context of the wound orrolled sorbent material sheets, especially those that are a single sheetwound in a spiral around a center or core, that this means that thesheets are not exactly the same distance apart from each other over theentire areas that face each other. Furthermore, it is understood that inthis context, similar variations in distance are contemplated betweenthe sheet or sheets due to components such as spacers, sensors,apertures, tubing, ports, valves, channels, corrugations, pleats, folds,deformation encountered during manufacturing or operation, deformationdue to the shape or pressures applied by or through the externalhousing, different wrapping techniques such as to seal the periphery ofthe sheets, and so forth.

As noted above with respect to the sorbent material sheets, the binderis selected from polytetrafluoroethylenes (PTFE or TEFLON),polyvinylidene fluorides (PVF2 or PVDF), ethylene-propylene-diene (EPDM)rubbers, polyethylene oxides (PEO), UV curable acrylates, UV curablemethacrylates, heat curable divinyl ethers, polybutylene terephthalate,acetal or polyoxymethylene resin, fluoroelastomers, perfluoroelastomers(FFKM) and/or tetrafluoro ethylene/propylene rubbers (FEPM), aramidpolymers, para-aramid polymers, meta-aramid polymers, poly trimethyleneterephthalate, ethylene acrylic elastomers, polyimide, polyamide-imides,polyurethanes, low density and high density polyethylene, polypropylene,biaxially oriented polypropylene (BoPP), polyethylene terephthalate(PET), biaxially oriented polyethylene terephthalate (BoPET),polychloroprene, and copolymers and combinations thereof

The Housing

The invention also contemplates the use of a housing which partially ortotally encapsulates the sorbent material sheets. It should be notedthat while the term “housing” is used in this specification to describethe overall outer structure that at least partially encapsulates thesorbent material sheets, it is understood that such structures are knownby many other terms to those of skill in the art. For example, inautomotive or other fields where emissions must be controlled, thehousing may be referred to as a canister, cartridge, scrubber, or thelike. It is therefore contemplated that the term “housing” broadlyencompasses a variety of terms and structures including canisters,cartridges, scrubbers, flexible bags, molded polymer casings, metalcasings, and so forth that are used in the field of emissions control.Furthermore the term housing may refer to a an empty structure awaitingthe inclusion of sorbent, i.e., an unfinished part, or a completedemissions control part that includes the sorbent contained within thecanister, cartridge, scrubber, flexible bag, etc. It is contemplatedthat these parts may be interchanged or combined depending on designrequirements.

One major advantage of the invention is that the sorbent material sheetsare both flexible and self-supporting and can be laminated, rolled,wound, folded, or stacked in a variety of configurations within thehousing to suit different mechanical requirements within the tightconfines of a vehicle. In such embodiments, the housing would bedesigned to conform or fit the spaces that are available for the deviceto be stored. For instance, the housing can be sized and shaped to fitin spaces within or surrounding wheel wells, driveshafts, batteries forhybrid powertrains, spare tires, tire changing tools, tire patchingtools, vehicle trunks or other storage spaces, vehicle bumpers andbodywork panels, exhaust systems, other emissions control equipment suchas urea or other injection tanks, fuel lines, vehicle frames, suspensioncomponents, engine compartment, under passenger compartment seats,within passenger compartment seats, and other spaces which are too smallor too difficult to reach to be effectively utilized for passenger orcargo space.

To further reduce weight and size and take advantage of theself-supporting sorbent material sheets, the housing can be in the formof a thin walled bag or pouch. This is possible because the sorbentmaterial sheets have some mechanical structure and are self-supportingand so do not require a rigid outer container as in conventionalcanisters. The film materials that form the bag can have thicknesses ofabout 10 μm to about 250 μm. In other embodiments, the bag film can havethicknesses of about 20 μm to about 175 μm, and the bag film can havethicknesses of about 50 μm to about 125 μm.

The bag or pouch may be formed of any materials which are used in fuelsystems, and particularly are formed of materials which are designed towithstand the chemical effects of the fuel vapors contained. Bagmaterials include polytetrafluoroethylenes (PTFE or TEFLON),polyvinylidene fluorides (PVF₂ or PVDF), ethylene-propylene-diene (EPDM)rubbers, polyethylene oxides (PEO), UV curable acrylates, UV curablemethacrylates, heat curable divinyl ethers, polybutylene terephthalate,acetal or polyoxymethylene resin, fluoroelastomers such asperfluoroelastomers (FFKM) and tetrafluoro ethylene/propylene rubbers(FEPM), aramid polymers such as para-aramid and meta-aramid polymers,poly trimethylene terephthalate, ethylene acrylic elastomers, polyimide,polyamide-imides, polyurethanes, low density and high densitypolyethylene, polypropylene, biaxially oriented polypropylene (BoPP),polyethylene terephthalate (PET), biaxially oriented polyethyleneterephthalate (BoPET), polychloroprene, and copolymers and combinationsthereof The bag is typically thermoplastic for flexibility, but can alsobe a combination with amounts of thermoset or can be in the form of acured rubber or an elastomer.

The housing, bag, or pouch may also be designed to act as a vaporbarrier to the adsorbed fuel vapors contained therein. This barrierproperty may be inherent to the polymer itself, or may be achievedthrough the use of at least one barrier additive and/or at least onebarrier layer. Examples of barrier additives which can be formed as alayer or as a particle filler include polymers such as epoxy, polyamide,polyamide imides, fluoropolymers, fluororubbers, and combinations ofthose. Barrier layers can also be made of metals such as aluminum,steel, titanium, and alloys of those. The metal barrier layers can beformed by conventional mechanical means, such as coextrusion or adheringwith the other layers of the housing, or they can be chemicallydeposited, such as by chemical vapor deposition or electroplating. Themetal barrier layer can be formed from a foil having a thickness of lessthan about 25 μm, less than about 20 μm, less than about 15 μm, lessthan about 10 μm, or less than about 5 μm.

The housing and its materials may also be selected to be compatible with“ship in a bottle” fuel systems. In such systems, many or all of thefuel system components, including the fuel pumps, ORVR, fuel filters,valves, and other components are fitted within the vehicle fuel tank.Such systems are advantageous because they reduce assembly time and theamount of space required by the fuel system. In such systems, thehousing should have materials which are capable of being immersed in theselected fuel, typically gasoline, for extended periods of time withinthe vehicle fuel tank, while also being able to withstand the effects ofthe adsorbed fuel vapors within.

The housing may also be a thin metal housing. The thin metal housing canbe formed of flexible or rigid metals such as steel, aluminum, titanium,and alloys of those. The metal housing can be formed from a foil havinga thickness of about 5-100 μm, or about 10-250 μm. In some embodiments,the foil may be as thick as about 1 mm. Whether the housing is flexibleor rigid depends on the selection of the material, the thickness, andany treatments that have been applied to the metals, such as heattreatments or hot or cold working.

In some embodiments, the housing for the sorbent material sheets may beomitted entirely, with the sorbent material sheets being containedwithin the fuel tank itself. In such configurations, the sorbentmaterials sheets can be attached to a portion of the interior of thefuel tank that does not regularly come in contact with liquid fuel andwhich is free to adsorb fuel vapors. This portion is typically the topor sides of the fuel tank, or combinations of those. The fuel tank mayalso include a recessed portion on the top or the sides which isdesigned to include the sorbent material sheets and allow the sorbentmaterial sheets to adsorb fuel vapors. Such embodiments where sorbentmaterial sheets are attached to the interior portions of the fuel tanknot only offer maximum space savings and weight savings by omitting thecanister structure, but also simplify manufacturing and installationbecause the sheets are already installed within the fuel tank duringvehicle assembly.

The housing can also be eliminated by forming a rolled or folded sorbentsheet and then selectively curing the outer sheets so that they form adurable, cured shell that acts as a support for the rolled or foldedsorbent sheets within. Such selective curing can be accomplishedthermally or with a chemical bath, or via actinic radiation, such asultraviolet light or by electron beam curing.

In embodiments where the sorbent material sheets omit the housing andare contained within the vehicle fuel tank itself, the sorbent materialsheets may be attached to the fuel tank in a variety of ways. Thesorbent material sheets can be fastened using mechanical fasteners suchas screws, rivets, or clamps, or the sorbent material sheets may befastened using an adhesive backing positioned between the fuel tank walland the sorbent material sheets. The adhesive backing may be a singlelayer of adhesive or a double sided adhesive tape or sheet. The adhesiveused in the adhesive backing may include pressure sensitive adhesives,UV curing adhesives, thermally curing adhesives, hot melt adhesives, andreactive multi-part adhesives. Adhesive compositions include acrylic and(meth)acrylic, acrylate and (meth)acrylate, epoxies in one- and two-partformulations, and urethane.

The sorbent material sheets may be applied during manufacturing in avariety of ways. In some embodiments, the fuel tank may be formed andthe sorbent material sheets are applied in a separate step where theadhesive is applied followed by the application of the sorbent materialsheets. In other embodiments, the sorbent material sheets are placed,with or without an adhesive backing as appropriate, on the inside of amold and the fuel tank is injected or blow molded around the sorbentmaterial sheets. In other embodiments, the sorbent material sheets maybe coextruded with panels of material which make up the sides of thefuel tank, and the edges of those panels are adhered or welded togetherto seal the final tank with the sorbent material sheets on the inside.

When the sorbent material sheets are contained within the vehicle fueltank without the housing, the fuel tank may include additional valvesand ports to accommodate the adsorption and desorption of fuel vapors inthe fuel tank. For example, during engine operation, air may beintroduced into the fuel tank to desorb the fuel vapors which arecontained in the sorbent material sheets, as well as those which arepresent in the tank. These desorbed fuel vapors are then sent to theengine for combustion during optimal cycles as required by the ECU.

When the sorbent material sheets are provided without a housing and arecontained within a tank, such as a vehicle fuel tank, they may bepositioned so that they are not regularly immersed in the volatileliquids typically contained within the tank. This ensures that thesorbent material sheets do not become prematurely saturated, and alsoensures that sufficient surface area is exposed to the vapors within thefuel tank to effect the adsorption of the vapors. The featurecontemplates that the sorbent material sheets can be placed in parts ofthe tank that are unfilled, such as the ullage or headspace of the tank,or near baffles which prevent the sloshing of liquids on the sorbentmaterial sheets. The sorbent material sheets may also be placed in adedicated portion of the tank, such as a small chamber or niche, wherethe liquids cannot enter.

The devices of various embodiments may include a housing and the sorbentmaterial sheets described above. The housing may be any shape and can beconfigured for purifying gasses or liquids. For example, in someembodiments, the housing may be any shape such as, for example,cuboidal, cubic, or cylindrical. The sorbent material sheets may besized to fit within the housing and substantially fill a space withinthe housing through which the gas or liquid is passed. In someembodiments, two or more sorbent material sheets may be stacked tosubstantially fill the housing, and in other embodiments, the sorbentmaterial sheets may be rolled to form a spiral wound sheet or pressed toform a stacked sheet. In some embodiments, the stacked or pressed sheetsmay be such that the sides of adjoining sheets are substantiallycontiguous. In other embodiments, stacked or pressed sheets may bepositioned such that adjoining sheets are spaced. For example, incertain embodiments, the sheets may be corrugated, having sorbentmaterial sheets that form a series or parallel ridges and furrows, andin some embodiments, corrugated sorbent material sheets may be separatedby flat sorbent material sheets. The corrugated sorbent material sheetsmay be disposed within the housing in a stacked or rolled/spiral woundform.

In various embodiments, the void fraction may be about 30% to about 32%less than the void volume for current devices, and in some embodiments,the void fraction may be less than 10%. For example, the devices mayhave a void fraction of about 45% to about 2%, about 35% to about 5%,about 25% to about 7%, or any individual void fraction or rangeencompassed by these example ranges. The devices of various embodimentsmay exhibit less flow restriction, e.g. pressure drop, than deviceshaving granular or pelleted sorbent materials. Thus, more adsorbentmaterial can be incorporated into such devices without reducing the flowrate of the device.

The devices of such embodiments may have BWCs of greater than about 5.0g/100 cm³, and in some embodiments, the devices may have a BWC of about4.0 g/100 cm³ to about 20 g/100 cm³, 5.0 g/100 cm³ to about 18 g/100cm³, about 7.0 g/100 cm³ to about 16 g/100 cm³, or about 8.0 g/100 cm³to about 15 g/100 cm³, or any individual BWC or range encompassed bythese example ranges. The devices may exhibit a pressure drop that is atmost equal to a conventional dense pack bed of powders, pellets, orgranules of activated carbon or other activated compounds. This featureis advantageous because it ensures that the inventive sorbent materialsheet product, whether stacked, rolled, wound, or otherwise configured,still has the same ability to process and transfer vapors and gases asconventional devices, despite the increased sorbent performance.

When the sorbent material product, stacked or rolled, is combined with ahousing, it is useful as a vapor loss canister or other device. As notedabove, the shapes and properties achieved via the stacked or rolledproducts allow for unique placement and improved performance.

In accordance with some embodiments, a vapor loss canister comprises ahousing having at least one sidewall defining an internal space, asorbent sheet product, such that the sorbent sheet media is sized andconfigured to fit within the housing and fill substantially the entireinternal space within the housing, wherein the internal space issubstantially free of additional internal material other than thesorbent sheet media. That is, traditional vapor loss canisters requiresprings, filters, support substrates, etc. to hold and maintain theloose carbon powder or pellets. Because the sorbent sheets aresubstantially self-supporting, these additional support structures arenot needed. This allows for the inclusion of more material or the use ofa smaller canister without sacrificing performance.

In some embodiments, the sorbent sheet product comprises a stackedsorbent sheet media comprised as described above. In such instances, thehousing or canister can take any shape as discussed above, but in someembodiments, is relatively flat and flexible for housing stacked sorbentsheet media that has a height substantially less than its length orwidth. In these instances, the housing may be a flexible bag or pouch,as discussed above.

In some instances the canister is adapted for placement atop or evenwithin a fuel tank.

In some embodiments, sorbent sheet material product comprises a rolledsorbent sheet product as described above. In some instances, at least aportion of the housing sidewall defines a filter substantially withoutoccupying any internal canister space.

In some embodiments, a fuel tank may be provided with integral vaporadsorption. Such tanks comprise a tank structure, and at least onesorbent sheet material product, either stacked or rolled, at least onefastening device which fastens the sorbent material product to a surfaceof the tank that is not regularly immersed in the volatile liquidscontained within the tank. The fastening device may be an adhesive layerwhich is formed between one surface of the sorbent material product anda wall of the tank.

Such adhesive may be at least one of pressure sensitive adhesives, UVcuring adhesives, thermally curing adhesives, hot melt adhesives,reactive multi-part adhesives, acrylic and (meth)acrylic adhesives,acrylate and (meth)acrylate adhesives, epoxies adhesives in one- andtwo-part formulations, urethane adhesives, and copolymers andcombinations thereof

The tank may further include one or more of at least one fuel pump(s),fuel sending line(s), fuel return line(s), atmospheric vent line,port(s), valve(s), sensor(s), air inlet(s), open cell foam, baffle(s),bladder(s) and combinations of those.

In some embodiments, the tank is a fuel tank with a “ship in a bottle”configuration.

Some embodiments provide an onboard refueling vapor recovery apparatuscomprising the sorbent material sheet product as described herein. Theonboard refueling vapor recovery apparatus may include a vapor adsorbingcanister as described herein. The onboard refueling vapor recoveryapparatus may include a tank with integral vapor adsorption.

Sorbent Material Sheets to Reduce Bleed Emissions

In some embodiments, the above sorbent materials sheets and housing areconfigured into a housing or canister to reduce, substantiallyeliminate, or eliminate bleed or breakthrough emissions that occur whenvapors escape from a volume of high adsorption capacity sorbent. Inthese embodiments, the vapor adsorbing canister includes at least afirst sorbent and a second sorbent. During an adsorption or desorptioncycle that coincides with fuel storage or engine operation, the firstsorbent adsorbs the majority of the fuel vapors, while the remainingvapors are scrubbed by the second sorbent. The scrubbing of theremaining vapors is key to controlling bleed emissions and achieving thelow emissions targets of current and future regulations.

The first and second sorbent may each be independently formed of anysorbent, to include conventional powder, pelleted, or granular forms.However, it is most advantageous that one or both of the first andsecond sorbent are formed of the sorbent material sheets or the sorbentmaterial sheet products that are described above. This enables thesignificant performance advantages to be used to solve the problem ofbleed emissions.

In some embodiments, the first sorbent and the second sorbent mayinclude sorbent sheets that include any of the sorbent materialsdescribed above including, but not limited to, activated carbon, naturaland synthetic zeolite, silica, silica gel, alumina, zirconia, ordiatomaceous earths. In certain embodiments, the sorbent material sheetsmay be composed of activated carbon. The above listed sorbents may beused alone or in combination.

One advantage of the present invention is that the high surface area andhigh density of the carbon that is incorporated into the first andsecond sorbents means that a canister can be designed that has both highretentivity and high adsorptive capacity. This is because in the priorart, carbon monoliths used for the second bleed chamber relied on highbinder loadings to create monoliths with greater voidage volume (i.e.,the amount of unoccupied space in a volume of material) to reducepressure drop. The disadvantage of high voidage is that it results inreduced adsorption performance and lower vapor-solid collisionefficiency. While the high binder content achieved the goal ofincreasing voidage and thereby affording a low pressure drop, it alsosacrifices adsorptive capacity because inert binder takes the place ofotherwise adsorptive sorbent. In some prior art monoliths, the amount ofactivated carbon sorbent is less than 50 wt. %, for instance, whichresults in larger devices and low adsorptive performance. In contrast,the higher density of the present sorbent material sheets, combined withinnovative arrangement of the sorbent material sheets, means that a muchsmaller device can be fabricated while still maintaining excellentoverall adsorptive capacity with a low pressure drop.

In some embodiments, the selection of the sheet form of adsorbentmaterial increases the apparent density versus granular, pelleted, orpowdered activated carbon by up to about 35%, up to about 30%, up toabout 25%, up to about 20%, up to about 15%, up to about 10%, or up toabout 5%. These increases in apparent density are computed by dividingthe apparent density of the sorbent material sheets over the apparentdensity of sorbent materials that are present in granular, pelleted, orpowdered forms. The apparent densities are measured using ASTM methodsD2854 and D8176.

In some embodiments, the first sorbent and the second sorbent may eachhave an incremental adsorption capacity of greater than about 35 gn-butane/L between vapor concentrations of 5 vol. % and 50 vol. % ofn-butane. This measurement is indicative of the improved performance ofthe sorbent that arises in part from the greater density of sorbentmaterial and the lesser amount of required binder. In some embodiments,the incremental adsorption capacity of the first sorbent or the secondsorbent is greater than about 35 g, greater than about 36 g, greaterthan about 37 g, greater than about 38 g, greater than about 39 g,greater than about 40 g, greater than about 41 g, greater than about 42g, greater than about 43 g, greater than about 44 g, greater than about45 g, greater than about 46 g, greater than about 47 g, greater thanabout 48 g, greater than about 49 g, greater than about 50 g, greaterthan about Mg, greater than about 52 g, greater than about 53 g, greaterthan about 54 g, greater than about 55 g, greater than about 56 g,greater than about 57 g, greater than about 58 g, greater than about 59g, greater than about 60 g, greater than about 61 g, greater than about62 g, greater than about 63 g, greater than about 64 g, greater thanabout 65 g, greater than about 66 g, greater than about 67 g, greaterthan about 68 g, greater than about 69 g, greater than about 70 g,greater than about 71 g, greater than about 72 g, greater than about 73g, greater than about 74 g, greater than about 75 g, greater than about76 g, greater than about 77 g, greater than about 78 g, greater thanabout 79 g, greater than about 80 g, greater than about 81 g, greaterthan about 82 g, greater than about 83 g, greater than about 84 g,greater than about 85 g, greater than about 86 g, greater than about 87g, greater than about 88 g, greater than about 89 g, greater than about90 g, greater than about 91 g, greater than about 92 g, greater thanabout 93 g, greater than about 94 g, greater than about 95 g, greaterthan about 96 g, greater than about 97 g, greater than about 98 g,greater than about 99 g, or greater than about 100 g, all measured byweight n-butane/L or sorbent between vapor concentrations of 5 vol. %and 50 vol. % of n-butane.

In some embodiments, the first sorbent and the second sorbent may eachhave an effective incremental adsorption capacity of greater than about35 g n-butane/L between vapor concentrations of 5 vol. % and 50 vol. %of n-butane. This measurement is indicative of the improved performanceof the sorbent that arises in part from the greater density of sorbentmaterial and the lesser amount of required binder. In some embodiments,the incremental adsorption capacity of the first sorbent or the secondsorbent is greater than about 35 g, greater than about 36 g, greaterthan about 37 g, greater than about 38 g, greater than about 39 g,greater than about 40 g, greater than about 41 g, greater than about 42g, greater than about 43 g, greater than about 44 g, greater than about45 g, greater than about 46 g, greater than about 47 g, greater thanabout 48 g, greater than about 49 g, greater than about 50 g, greaterthan about 51 g, greater than about 52 g, greater than about 53 g,greater than about 54 g, greater than about 55 g, greater than about 56g, greater than about 57 g, greater than about 58 g, greater than about59 g, greater than about 60 g, greater than about 61 g, greater thanabout 62 g, greater than about 63 g, greater than about 64 g, greaterthan about 65 g, greater than about 66 g, greater than about 67 g,greater than about 68 g, greater than about 69 g, greater than about 70g, greater than about 71 g, greater than about 72 g, greater than about73 g, greater than about 74 g, greater than about 75 g, greater thanabout 76 g, greater than about 77 g, greater than about 78 g, greaterthan about 79 g, greater than about 80 g, greater than about 81 g,greater than about 82 g, greater than about 83 g, greater than about 84g, greater than about 85 g, greater than about 86 g, greater than about87 g, greater than about 88 g, greater than about 89 g, greater thanabout 90 g, greater than about 91 g, greater than about 92 g, greaterthan about 93 g, greater than about 94 g, greater than about 95 g,greater than about 96 g, greater than about 97 g, greater than about 98g, greater than about 99 g, or greater than about 100 g, all measured byweight n-butane/L or sorbent between vapor concentrations of 5 vol. %and 50 vol. % of n-butane.

In some embodiments, the first sorbent and the second sorbent may eachhave a nominal incremental adsorption capacity of greater than about 35g n-butane/L between vapor concentrations of 5 vol. % and 50 vol. % ofn-butane. This measurement is indicative of the improved performance ofthe sorbent that arises in part from the greater density of sorbentmaterial and the lesser amount of required binder. In some embodiments,the incremental adsorption capacity of the first sorbent or the secondsorbent is greater than about 35 g, greater than about 36 g, greaterthan about 37 g, greater than about 38 g, greater than about 39 g,greater than about 40 g, greater than about 41 g, greater than about 42g, greater than about 43 g, greater than about 44 g, greater than about45 g, greater than about 46 g, greater than about 47 g, greater thanabout 48 g, greater than about 49 g, greater than about 50 g, greaterthan about 51 g, greater than about 52 g, greater than about 53 g,greater than about 54 g, greater than about 55 g, greater than about 56g, greater than about 57 g, greater than about 58 g, greater than about59 g, greater than about 60 g, greater than about 61 g, greater thanabout 62 g, greater than about 63 g, greater than about 64 g, greaterthan about 65 g, greater than about 66 g, greater than about 67 g,greater than about 68 g, greater than about 69 g, greater than about 70g, greater than about 71 g, greater than about 72 g, greater than about73 g, greater than about 74 g, greater than about 75 g, greater thanabout 76 g, greater than about 77 g, greater than about 78 g, greaterthan about 79 g, greater than about 80 g, greater than about 81 g,greater than about 82 g, greater than about 83 g, greater than about 84g, greater than about 85 g, greater than about 86 g, greater than about87 g, greater than about 88 g, greater than about 89 g, greater thanabout 90 g, greater than about 91 g, greater than about 92 g, greaterthan about 93 g, greater than about 94 g, greater than about 95 g,greater than about 96 g, greater than about 97 g, greater than about 98g, greater than about 99 g, or greater than about 100 g, all measured byweight n-butane/L or sorbent between vapor concentrations of 5 vol. %and 50 vol. % of n-butane.

While the disclosure mentions first sorbents and second sorbents, it isunderstood that modifications and alternatives to this construction arecontemplated. For example, each of the first sorbent and the secondsorbent may actually include multiple bodies of sorbent in differentforms or combinations. Thus, there can be first sorbents, secondsorbents—third sorbents, fourth sorbents, and so on.

Additional Components

The invention may include sensors such as a fuel composition sensor. Thefuel composition sensor may be used to detect the mixture of gasolineand ethanol contained within the housing and the sorbent material, andthis information may be communicated to the ECU so that vapors which arelater released to the engine can be more precisely used during enginecombustion. Other sensors include temperature sensors, vapor pressuresensors, oxygen sensors, and the like. The sensors can operate onprinciples of electrochemical interaction, electronic such asthermocouples, electromechanical, refractive index, infraredspectroscopy, and others depending on the type of information that isrequired for the ECU. The sensors can be included alone or incombination within the housing, or, if no housing is specified, withinthe area that contains the sorbent materials sheets. The sensors can beincluded in holes or notches which are cut from the sheet, or in spacesbetween the sheets with the sheets wrapped or folded around the sensors.

The invention may include inlets, outlets, hoses, and associated valvesto control the flow of fuel vapor to and from the sorbent materials ofthe invention. The openings may be static or they may have valves thatare opened and closed as required by the ECU to control the flow ofvapor into and out of the sorbent sheets of the invention. For example,during refueling, outlet valves remain closed to ensure that displacedfuel vapors do not escape into the atmosphere. However, when the engineoperates and the ECU requests it, at least one outlet valve may open toallow the release of adsorbed vapor into the engine to allow itscombustion. There may also be included a vent and valve to theatmosphere in case there is too much fuel vapor for the sorbent materialsheets of the invention to safely adsorb. There may further be includedan inlet and valve for air or other gases, such as inert exhaust gases,which is used to desorb the fuel vapor as it is being sent to the enginefor combustion.

The invention also contemplates the inclusion of and integration withother components which make up ORVR systems and devices. These othercomponents may include active compressors and condensers, fuel tankheaters, fuel tank heat exchanging coils for cooling enclosed fuels,fuel filler necks, fuel filler ports, including capless fuel fillerports, vents for fuel vapors, fuel lines for sending fuel, fuel returnlines, vents and vehicle rollover valves, fuel pumps, and air intake orpurge valves.

The invention further contemplates devices and structures which may becombined with the sorbent material sheets to improve or control theadsorption and desorption of fluids and gases. For example, fans orpumps may be included to force the fluids or vapors over the sorbentmaterial sheets as they are assembled, allowing the sorbent materialsheets to be packed or wound tighter or allowing larger devices thanwould otherwise be possible with the same amount of fluid diffusion overthe sheets. Alternatively, the devices can include resistance elementheaters, or Peltier effect heaters or coolers which are designed to heatand/or cool the fluids and thus force their movement over the sorbentmaterial sheets of the claimed invention. For instance, heated,expanding fluid may vent upwards and draw in more fluid at the bottom ofa rolled or wound article that is oriented vertically to take advantageof the effects of gravity.

Other Uses

In addition to automotive uses, the inventors contemplate that thesorbent sheets of the claimed invention can be used in any instancewhere a tank or other enclosed space is designed to contain volatileliquids, in particular volatile hydrocarbons such as fuels, solvents,and other volatile compounds. Examples include but are not limited tofuel tanks in aircraft, fuel tanks in ships and other marine vehicles,fuel tanks in trucks, chemical tanks in railroad cars, barges, ships,trucks, vehicles, and other bulk carriers, and stationary chemicaltanks. The sorbent material sheets of the claimed invention can also beattached or adhered to the walls of confined spaces where the presenceof volatile compounds would be detrimental, for example, in chemicalfacilities where operators and maintenance staff must periodicallyaccess the space. Such sorbent material sheets, when used in suchcombined spaces, can not only increase safety for operators andmaintenance staff, but they can also reduce the need for cumbersomeprotective gear.

EXAMPLES

Although the present invention has been described in considerable detailwith reference to certain preferred embodiments thereof, other versionsare possible. Therefore the spirit and scope of the appended claimsshould not be limited to the description and the preferred versionscontained within this specification. Various aspects of the presentinvention will be illustrated with reference to the followingnon-limiting examples.

As was discussed above, BWC is a measure of the performance of activatedcarbon. BWC is determined for a sample by measuring the ability of theactivated carbon to adsorb and desorb butane from dry air underspecified conditions, and measures the difference between the butaneadsorbed at saturated and the butane retained per unit volume of carbonafter a specified purge. BWC can be tested in several ways, includingprocedures specified by ASTM International and which are known to thoseof skill in the art. Specifically, testing can follow ASTM D5228, whichincludes revisions D5228-16, D5228-92(2015), D5228-92(2005), andD5228-92(2000).

In Examples 1-4, the carbon sheets were spiral wound to yield 10% voidfraction, which give about a 30% performance improvement over theactivated carbons in their original, non-sheet form. The void fractionof comparative granular or powdered beds of activated carbon, similar toComparative Example 1, was approximately 40% void fraction by volume.The Examples and Comparative Example are described below.

Example 1

Activated carbon sheets were made from CPL (CT#14299-8), which is anactivated carbon that is wood based and which is activated usingphosphoric acid. Sheets were also made from CPW (CT#14299-10), which isan activated carbon that is wood based and which is activated usingphosphoric acid. The activated carbons were pulverized in a mechanicalmortar and pestle and mixed with 9% PTFE powder. The resultingcomposition had a bread dough-like consistency. The composition wasrolled to form sheets having thicknesses of 0.448 mm (CT#14299-8 1),0.411 mm (CT#14299-8 2), 0.459 mm (CT#14299-10 1), and 0.439 mm(CT#14299-10 2).

Example 2

Activated carbon sheets were prepared as described in Example 1 usingBVC-11 8×25 activated carbon, which is a nutshell based activated carbonthat is activated with phosphoric acid. This formed sample CT#14266-1. Asample was also formed with BVC-11 8×35, which is also a nutshell basedactivated carbon that is activated with phosphoric acid. This formedsample CT#14266-2. The formed sheets had a thickness of 0.330 mm(CT#14266-11), 0.334 mm (CT#14266-1 2), 0.327 mm (CT#14266-1 3), 0.317mm (CT#14266-2 1), 0.307 mm (CT#14266-2 2), and 0.328 mm (CT#14266-2 3).As used herein, GAC is used to denote granular activated carbon, and PACis used to denote powdered activated carbon.

Butane Working Test—Examples 1 and 2

Activated carbon sheets prepared in Examples 1 and 2 were tested forbutane adsorption using the butane working test. In this test, thesheets were rolled and placed in tubes. Butane was added to the tubesand butane adsorption was measured. Results are illustrated in TABLES 1and 2:

TABLE 1 (Example 2) 14266-1 14266-2 Tube vol. (cm³) 3.85 3.85 Sheet wt.(g) 6.3604 6.0009 Sheet thick. (mm) 0.330 0.315 Sheet vol. (cm³) 11.2210.71 Sheet dens. (g/cm³) 0.567 0.567 BWC sheet 16.10 14.14 measured(g/100 cm³) BWC GAC 12.10 12.20 measured (g/100 cm³)

TABLE 2 (Example 1) CT-14299-8 CT-14299-10 Tube vol. (cm³) 16.504 16.504Sheet wt. (g) 4.10 3.16 Sheet thick. (mm) 0.411 0.439 Sheet vol. (cm³)9.92 7.90 Sheet dens. (g/cm³) 0.413 0.404 BWC sheet 12.32 12.41 measured(g/100 cm³) BWC PAC 7.9 9.6 measured (g/100 cm³)

Example 3

Activated carbon sheets were prepared as in Examples 1 and 2, but usinggranular activated carbon #3445-32-4. The activated carbon sheets werealso not rolled as tightly as in prior Examples 1 and 2, which Theresultant sheets were tested for butane adsorption using the BWC test.In these two tests, two separate stacks of 20 sheets of 0.45mm thicknesswere cut in rectangles of 2.2 cm×7.5 cm±10%, sealed at the side edgewith double sided tape of 0.05mm thickness and 2mm width. In thisconfiguration, tape thickness defined the average sheet spacing. Totalheight of each of the stacks of 20 sheets with tape spacers was 1 cm.These stacks of sheets were then placed in large 2.54 cm diametercylindrical glass tubes for butane adsorption/desorption testing. Theexcess volume between the rectangular stack of sheets and the walls ofthe cylindrical glass tube were filled with closed cell expanded foam totake up the excess volume and sealed to avoid bypass gas flow past theinserted test samples. The butane or air was forced to flow in the 0.05mm gaps between the 20 sheets. The flow rate and volume of the stacks ofsheets was selected to conform to the BWC procedure. The BWC procedurewas followed with the exception of the use of the stack of sheets ratherthan a granule bed, the use of the closed cell expanded foam forsealing, and the required larger cylindrical glass tube arrangement toaccommodate the rectangular stack of sheets.

During the BWC procedure on the sheet stack, butane or air was forced toflow in the 0.05 mm gaps between the 20 sheets, with the flow rate andvolume of the stacks of sheets kept to BWC procedure for workingcapacity. The results of Example 3 are in Table 3 below.

Comparative Example 1

A comparative example was also prepared using the same granularactivated carbon #3445-32-4 as in Example 4, but without forming thegranular activated carbon as part of a sheet or roll. The granulatedactivated carbon was tested per BWC procedure. The results of this testare in Table 3 below.

TABLE 3 (Example 3 and Comparative Example 1) Stacked 0.45 mm sheetsGranular activated carbon (Example 3) (Comparative Example 1) #3445-32-#3445-32-4- #3445-32-4 4-stack 1 stack 2 Tube vol. minus 16.7 16.4 15.5foam volume if present(cm³) Carbon wt. (g) 6.513 7.885 7.465 Sheetthickness — 0.45 0.45 (mm) Granular bed or 16.7 16.4 15.5 Stacked sheetvol. (cm³) Granular bed or 0.389 0.534 0.534 individual Sheet density(g/cm³) BWC (g/100 cm³) 9.33 10.25 10.83 BWC % — 9.9% 16.0% improvement

Conclusion and Summary of Examples 1-3 and Comparative Example 1

A summary of relevant data appears in Table 4 below:

TABLE 4 Summary of Data Sheet BWC Thickness Density (g/100 Example TestDescription (mm) (g/cm³) cm³) Ex. 1 CT#14299-8 Wood based 0.411 0.41312.32 activated carbon CPL Ex. 1 CT#14299- Wood based 0.439 0.404 12.4110 activated carbon CPW Ex. 2 CT#14266-1 BVC-11 0.330 0.567 16.10(nutshell) activated carbon 8 × 25 Ex. 2 CT#14266-2 BVC-11 0.315 0.56714.14 (nutshell) activated carbon 8 × 35 Ex. 3 #3445-32-4- GAC, 20 0.450.534 10.25 stack 1 sheet stack Ex. 3 #3445-32-4 GAC, 20 0.45 0.53410.83 stack 2 sheet stack Comp. Ex. 1 #3445-32-4 Granular N/A 0.389 9.33Activated Carbon (GAC)

1. A vapor adsorbing canister comprising: a first sorbent; a secondsorbent; and wherein during an adsorption or a desorption operation, thelinear velocity of gases is higher in the second sorbent than in thefirst sorbent; and wherein the first sorbent and the second sorbent eachindividually have an incremental adsorption capacity of greater than 35g n-butane/L between vapor concentrations of 5 vol. % and 50 vol. %n-butane.
 2. The vapor adsorbing canister of claim 1, wherein: each ofthe first sorbent and the second sorbent include a binder that comprisespolytetrafluoroethylenes (PTFE or TEFLON), polyvinylidene fluorides(PVF₂ or PVDF), ethylene-propylene-diene (EPDM) rubbers, polyethyleneoxides (PEO), UV curable acrylates, UV curable methacrylates, heatcurable divinyl ethers, polybutylene terephthalate, acetal orpolyoxymethylene resin, fluoroelastomers, perfluoroelastomers (FFKM)and/or tetrafluoro ethylene/propylene rubbers (FEPM), aramid polymers,para-aramid polymers, meta-aramid polymers, poly trimethyleneterephthalate, ethylene acrylic elastomers, polyimide, polyamideimides,polyurethanes, low density and high density polyethylene, polypropylene,biaxially oriented polypropylene (BoPP), polyethylene terephthalate(PET), biaxially oriented polyethylene terephthalate (BoPET),polychloroprene, or copolymers or combinations thereof, and wherein thebinder of the first and the second sorbent is the same or different. 3.The vapor adsorbing canister of claim 1, wherein the first sorbent andthe second sorbent each individually include less than or equal to about20 wt. % of binder.
 4. The vapor adsorbing canister of claim 3, whereinthe first sorbent and the second sorbent each individually includegreater than or equal to about 80 wt. % of sorbent material.
 5. Thevapor adsorbing canister of claim 1, wherein the first sorbent and thesecond sorbent each individually include less than or equal to about 10wt. % of binder.
 6. The vapor adsorbing canister of claim 5, wherein thefirst sorbent and the second sorbent each individually include greaterthan or equal to about 90 wt. % of sorbent material.
 7. The vaporadsorbing canister of claim 1, wherein the second sorbent is in the formof a sheet.
 8. The vapor adsorbing canister of claim 1, wherein thesecond sorbent is in the form of a sheet that is corrugated, textured,folded, has apertures, wrapped in an “S” shape, in a convex “C” shape,in a concave “C” shape, rolled, has spacers between multiple sheets, andcombination of the above features.
 9. The vapor adsorbing canister ofclaim 1, wherein the second sorbent is in the form of a sheet, saidsheet including sorbent particles having an average particle diameter ofabout 0.001 mm to about 0.2 mm.
 10. The vapor adsorbing canister ofclaim 1, wherein the second sorbent is in the form of a sheet havingraised and/or depressed portions.
 11. The vapor adsorbing canister ofclaim 10, wherein the raised and/or depressed portions are present onadjacent sheets and are nested.
 12. The vapor adsorbing canister ofclaim 10, wherein the raised and/or depressed portions are present onadjacent sheets and are not nested.
 13. The vapor adsorbing canister ofclaim 1, wherein the second sorbent is in the form of a sheet having avoid volume of about 10% or more.
 14. The vapor adsorbing canister ofclaim 1, wherein the second sorbent is in the form of a sheet having adensity of about 0.08 g/cm³ to about 1.5 g/cm³.
 15. The vapor adsorbingcanister of claim 1, wherein the first sorbent and the second sorbentare each separately selected from the group consisting of activatedcarbon, natural and synthetic zeolite, silica, silica gel, alumina,zirconia, diatomaceous earths, and combinations thereof.
 16. The vaporadsorbing canister of claim 1, further comprising a housing.
 17. Thevapor absorbing canister of claim 16, wherein the housing is flexible.18. The vapor adsorbing canister of claim 17, wherein the housing isselected from the group consisting of polytetrafluoroethylenes (PTFE orTEFLON), polyvinylidene fluorides (PVF₂ or PVDF),ethylene-propylene-diene (EPDM) rubbers, polyethylene oxides (PEO), UVcurable acrylates, UV curable methacrylates, heat curable divinylethers, polybutylene terephthalate, acetal or polyoxymethylene resin,fluoroelastomers perfluoroelastomers (FFKM) and/or tetrafluoroethylene/propylene rubbers (FEPM), aramid polymers, para-aramid,meta-aramid polymers, poly trimethylene terephthalate, ethylene acrylicelastomers, polyimide, polyamide-imides, polyurethanes, low density andhigh density polyethylene, polypropylene, biaxially orientedpolypropylene (BoPP), polyethylene terephthalate (PET), biaxiallyoriented polyethylene terephthalate (BoPET), polychloroprene, copolymersthereof, and combinations thereof
 19. The vapor adsorbing canister ofclaim 1, further comprising at least one structure selected from tubes,inlet ports, outlet ports, sensors, valves, and fluid channels.
 20. Anonboard refueling vapor recovery apparatus comprising the vaporadsorbing canister of claim 1.